Dye compounds

ABSTRACT

This invention relates to new fluorescent or non-fluorescent dye compounds having a terminal hydroxy, carboxylic acid/ester or amino group and a process for their preparation. The new fluorescent or non-fluorescent dye compounds are useful as colorants for preparing colored synthetic polymer resins with pigmentary properties, for dyeing or printing homo- or mixed synthetic, semi-synthetic or natural polymers or substrates or for preparing inks. The dye compounds provide excellent properties, especially high temperature stability and easy applicability.

This invention relates to new fluorescent or non-fluorescent dyemolecules having a terminal hydroxy, carboxylic acid/ester or aminogroup.

BACKGROUND

Articles containing colorants are known to loose their colour whenexposed to solar radiation for extended times. In particular,fluorescent colorants degrade more quickly than conventional colorants,often turning colourless on exposure to daily solar radiation withindays or months.

Colorants not covalently bond in a polymer matrix tend to agglomerateand to crystalize leading to inhomogeneous distribution of colorantswithin the matrix. Fluorescent colorants in particular often loose theirfluorescent properties by agglomeration of fluorescent sites(quenching). Furthermore with non covalently bond colorants, fading orbleeding of the colorant occurs.

U.S. Pat. No. 6,103,006 (DiPietro) discloses fluorescent polymericpigments with increased lightfastness obtained by the polycondensationof dye monomers with at least two functional groups like diamine,dialcohol or dicarboxylic acid. The functional groups for thepolycondensation are directly located at the dye moiety as in theanhydride or diacid form of the BXDA fluorescent dye.

Besides the above mentioned polycondensation process the polyreaction ofchain growth polymers can be utilised to react dye monomers into apolymer backbone. WO 99/21937 (3M) discloses a two phaseinterpenetrating polymer network system with a dye functionalizedpolymer in the second phase. The optionally fluorescent dye iscovalently bond to the polymer to slow migration and to enhancecompatibility, e.g. a hydroxy functional dye (YGOH) is reacted into apolyurethane or an acrylate functional dye (YGOAcr) is reacted into arespective chain growth polymer.

Other structures known to have dye properties are disclosed in WO00/31039 in a completely different context: as pharmaceutically activecompounds for the control of thrombotic disorders and for use asanti-adhesive substances for implants, catheters or heart pacemakers.The substituents are selected in view of pharmaceutical activity andapplicability and the substituted benzo[de]isoquinoline-1,3-diones arenot supposed to have any connective function.

SUMMARY OF THE INVENTION

One objective of the present invention is to provide new dye compoundsthat have a connective functionality attached to the dye moiety by aspacer of a chain length of C₃ or longer. The dye compounds are usefuluseful as colorants for preparing colored synthetic polymer resins withpigmentary properties, for dyeing or printing homo- or mixed synthetic,semi-synthetic or natural polymers or substrates or for preparing inks.

DETAILED DESCRIPTION OF THE INVENTION

The dye compound is of the general formula (I)

in which R₁ is C₃₋₁₂ alkylen, C₂ alkoxy alkylene, C₆₋₁₀ arylen, (C₆₋₁₀)aryl-(C₁₋₆) alkylen or (C₁₋₆) alkyl-(C₆₋₁₀) arylen, the alkylen and/orarylen radicals optionally being substituted by hydroxyl, C₁₋₆ alkoxyl,C₆₋₁₀ aryloxy or halogen,

X is hydroxy, COOR′ or NHR′ with R′ being hydrogen, C₁₋₆ alkyl, C₆₋₁₀aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₁₋₆) alkyl-(C₆₋₁₀) aryl, the alkyland/or aryl radicals optionally being substituted by hydroxyl, C₁₋₆alkoxyl, C₆₋₁₀ aryloxy or halogen,

A is a substituted or unsubstituted fused aromatic or heterocyclic ringsystem, preferably of the general formula (III), (IV), (V), (VI), (VII)or (VIII)

wherein R₃ is hydrogen, halogen, NR₄R₅, R₄O or R₄S, with R₄ beinghydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₁₋₆)alkyl-(C₆₋₁₀) aryl, the alkyl and/or aryl radicals optionally beingsubstituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen,subsequently R₅ being hydrogen, C₂₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀)aryl-(C₁₋₆) alkyl or (C₃₋₆) alkyl-(C₆₋₁₀) aryl, the alkyl radicalsoptionally being substituted by C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen,the aryl radicals optionally being substituted by hydroxyl, C₁₋₆alkoxyl, C₆₋₁₀ aryloxy or halogen, with the provisio that R₄ is to bechosen first and if R₄ is hydrogen, R₅ can only be hydrogen; Y beingsulphur, oxygen or NR₄, with R₄ having the meaning given above,

R₆ and R₇ are identical or different and are hydrogen, C₁₋₆alkyl,C₆₋₁₀aryl, (C₆₋₁₀)aryl-(C₁₋₆)alkyl or (C₁₋₆)alkyl-(C₆₋₁₀)aryl, it beingpossible for the alkyl and/or aryl radicals to be substituted byhydroxyl, C₁₋₆alkoxy, C₆₋₁₀aryloxy or halogen and

p and q are 0-12

Another dye compound is of the general formula (II)

wherein R₁ and X have the meaning given above,

with the proviso that for X being NH₂, R₁ being C₆ alkylen is excludedand with the proviso that for X being OH, R₁ being C₃ alkylen isexcluded.

Especially preferred dye compounds are those of the general formula (I)where A is of the general formula (IV), with Y being sulphur and R₃being hydrogen, where A is of the general formula (VI) with R₃ beinghydrogen, where A is of the general formula (VII) with R₃ being hydrogenand where A is of the general formula (VIII) with R₆ and R₇ being methyland p and q being 1.

The preferred spacer R₁ is a C₃₋₆ alkylen, most preferably C₆ alkylen.Another preferred spacer R₁ is a ethoxy-ethoxy-ethylene.

Preferred terminal groups X are hydroxy or NHR′ with R′ being preferablyhydrogen, methyl or ethyl.

The dye compounds of formulae (I) are obtained by the condensation ofthe dicarboxylic anhydride of the respective dye moiety with anaminoalcohol, an aminoacid/ester or a diamine comprising the respectivespacer in a polar aprotic solvent.

The hydroxy, carboxylic acid/ester or amino group on the free end of thespacer can be reacted into a polymer network, e.g. polyurethane,polyester or aminoformaldehyde resin.

To obtain such colored polymer resins, the dye compound is mixed into arespective reactive mixture comprising isocyanates or formaldehyde andoptionally other carboxy, hydroxy or amine functionalized compoundsbefore the reaction is carried out. The polyreactions to obtainpolyurethane, polyester or aminoformaldehyde resins are well known inthe art.

The dye compounds according to the invention may be used for dyeingdyeable materials such as homo- or mixed synthetic, semi-synthetic ornatural polymers e.g. acrylonitrile, polyester, polyurethane, polyamide,wool, leather, cotton, bast fibers such as hemp, flax, sisal, jute, coirand straw; regenerated cellulose fibers, glass or glass productscomprising glass fibers; and substrates comprising cellulose for examplepaper and cotton. They may also be used for printing fibers, filamentsand textiles comprising any of the above mentioned materials inaccordance with known methods. The compounds of the present inventionmay be further used in the preparation of inks, e.g. ink jet inks inaccordance with conventional methods.

The colored polymer resins are suitable for the mass pigmentation ofsynthetic resins, e.g. polyurethane masses, polyester oraminoformaldehyde resins.

The obtained resins are suitable, as colorants in powders and powdercoating materials, especially in triboelectrically or electrokineticallysprayable powder coating materials which are used for the surfacecoating of articles made, for example, from metal, wood, plastic, glass,ceramic, concrete, textile material, paper or rubber.

Powder coating resins that are typically employed are epoxy resins,carboxyl- and hydroxyl-containing polyester resins, polyurethane resinsand acrylic resins, together with customary hardeners. Combinations ofresins are also used. For example, epoxy resins are frequently employedin combination with carboxyl- and hydroxyl-containing polyester resins.Typical hardener components (as a function of the resin system) are, forexample, acid anhydrides, imidazoles and also dicyanodiamide and itsderivatives, blocked isocyanates, bisacylurethanes, phenolic andmelamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylicacids.

The following examples illustrate the invention. Unless otherwisespecified, parts and percentages used in the examples are on a weight toweight basis.

Example 1

Benzothioxanthene dicarboxylic anhydride (10 parts) is condensed to6-aminohexanol (6 parts) in dimethylformamide (6 parts) in presence ofcatalytic para-toluenesulfonic acid (0.1 part) at 130° C. under nitrogenatmosphere.

When the reaction is complete, the resulting mixture is cooled to 60° C.and 3 parts of methanol are added. After cooling to room temperature,the final product is filtered, washed with methanol and dried. 12 partsof bright orange powder are obtained (93% yield).

Example 2

57 parts of hexamethylenediamine are melted at 80° C. under nitrogenatmosphere. 10 parts of benzo[k,l]-thioxanthene-3,4-dicarboxylic acidanhydride are added over a 3 hours period at this temperature. Aftercompletion of the addition, the resulting fluorescent suspension isstirred for 2 hours at 80° C. 250 parts of water are then introduced atthis temperature and the reaction mixture is stirred for one hour. Themixture is then added to 250 parts of hot water (80° C.). The finalsuspension is filtered at this temperature, washed with hot water (80°C.) and then dried. 12 parts of final colorant are obtained as anorange-colored powder.

Example 3

2,2′-(ethylenedioxy)-diethylamine (40 parts) are heated to 70° C. undernitrogen atmosphere. Benzothioxanthene anhydride (10 parts) is slowlyadded at this temperature over a period of 3 hours. After reactioncompletion, 40 parts of water are added and the resulting mixture isstirred at 70° C. for 30 minutes. The suspension is then filtered,washed with water and dried. 10 parts of orange powder are obtained(yield 80%).

Example 4

45 parts of hexamethylenediamine are melted at 80° C. under nitrogenatmosphere. 10 parts of perylene dicarboxylic acid anhydride are addedover a 3 hours period at this temperature. After completion of theaddition the resulting suspension is stirred for 2 hours at 80° C. 200parts of water are then introduced at this temperature and the reactionmixture is stirred for one hour. The mixture is then added to 200 partsof hot water (80° C.). The final red suspension is filtered at thistemperature, washed with hot water (80° C.) and then dried. This gives13 parts of a red-colored powder.

Example 5

10 parts of perylene tetracarboxylic acid dianhydride and 5.7 parts ofpotassium hydroxide are suspended in 150 parts of water. The redsuspension is heated to 100° C. and stirred at this temperature for 1hour. The reaction mixture is cooled to 80° C. and hydrochloric acid isadded until pH reached 7. The suspension is then stirred at 80° C. for30 minutes, cooled to 25° C., washed with water and dried. 10 parts ofthe resulting red powder are suspended in 4 parts of o-phenylenediamine,3 parts of zinc acetate and 1 part of chinolin. The reaction mixture isheated to 200° C. and stirred for 2 hours at this temperature. Aftercooling to 25° C. the reaction mixture is filtered and washed withmethanol and then with water. Hydrochloric acid is added to 10 parts ofthe resulting red powder firstly suspended in 100 parts of water, inorder to reach pH 1. The reaction mixture is stirred 30 minutes at 100°C., filtered and washed with water. 10 parts of the presscake are addedover a 3 hours period to 20 parts of melted hexamethylenediamine at 100°C. under nitrogen atmosphere. The reaction mixture is stirred 4 hours at100° C. and precipitated in 200 parts of hot water. The reaction mixtureis then filtered at 80° C., washed with hot water and dried to provide10 parts of a red-colored powder.

Example 6

10 parts of perylene tetracarboxylic acid dianhydride and 5.7 parts ofpotassium hydroxide are suspended in 150 parts of water. The redsuspension is heated to 100° C. and stirred at this temperature for 1hour. The reaction mixture is cooled to 80° C. and hydrochloric acid isadded until pH reached 7. The suspension is then stirred at 80° C. for30 minutes, cooled to 25° C., washed with water and dried. 10 parts ofthe red powder are suspended in 15 parts of water and 4 parts of1,3-diamino-2,2-dimethylpropane. The reaction mixture is heated toreflux for 2 hours. After cooling to 25° C. the reaction mixture isfiltered and washed with water. Hydrochloric acid is added to 10 partsof the resulting red presscake firstly suspended in 100 parts of water,in order to reach pH 1. The reaction mixture is stirred 30 minutes at100° C., filtered and washed with water. 10 parts of the presscake areadded over a 3 hours period to 20 parts of melted hexamethylenediamineat 100° C. under nitrogen atmosphere. The reaction mixture is stirred 4hours at 100° C. and precipitated in 200 parts of hot water. Thereaction mixture is then filtered at 80° C., washed with hot water anddried to provide 12 parts of a red-colored powder.

Example 7

35 parts of tetramethylenediamine are melted at 100° C. under nitrogenatmosphere. 10 parts of perylene tetracarboxylic acid dianhydride areadded over a 3 hours period at this temperature. The resulting redsuspension is stirred for 6 hours at 100° C. 100 parts of 5% potassiumhydroxide solution in water are then introduced at this temperature andthe reaction mixture is stirred for 30 minutes. The suspension is thenfiltered at 80° C., washed with hot water (80° C.) and then dried. Thisgives 12 parts of a red-colored powder.

Example 8

Perylene tetracarboxylic dianhydride (10 parts) is condensed to3-methylamino propylamine (25 parts) in ethanol (2.5 parts) undernitrogen atmosphere at 90° C. When reaction is complete, the mixture iscooled to room temperature and filtered. The dark red presscake ispoured into 100 parts of water and stirred for 30 minutes at 70° C.After filtration and washing with water, the product is dried and 11parts of dark red powder are obtained (93% yield).

Example 9

2,2′-(ethylenedioxy)-diethylamine (40 parts) are heated to 80° C. undernitrogen atmosphere. Perylene tetracarboxylic dianhydride (10 parts) isslowly added at this temperature over a period of 3 hours. When thereaction is complete, the mixture is cooled to room temperature andfiltered. The dark red presscake is poured into 100 parts of water andstirred for 30 minutes at 70° C. After filtration and washing withwater, the product is dried and 15.5 parts of dark red powder areobtained (93% yield).

What is claimed is:
 1. A dye compound of the general formula (I)

wherein R₁ is C₆ alkylene, or ethoxy-ethoxy-ethylene, X is hydroxy,COOR′ or NHR′ group with R′ being hydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl,(C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₁₋₆) alkyl-(C₆₋₁₀) aryl, the alkyl and/oraryl radicals optionally being substituted by hydroxyl, C₁₋₆ alkoxyl,C₆₋₁₀ aryloxy or halogen, and A is of the general formula, (IV), (V),(VI), (VII) or (VIII)

wherein R₃ is hydrogen, halogen, NR₄R₅, R₄O or R₄S, in which R₄ ishydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₁₋₆)alkyl-(C₆₋₁₀) aryl, the alkyl and/or aryl radicals optionally beingsubstituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen, R₅ ishydrogen, C₂₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₃₋₆)alkyl-(C₆₋₁₀) aryl, the alkyl radicals optionally being substituted byC₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen, the aryl radicals optionallybeing substituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen,with the provisio that R₄ is to be chosen first and if R₄ is hydrogen,R₅ can only be hydrogen; Y being sulphur, oxygen or NR₄, with R₄ havingthe meaning given above, R₆ and R₇ are identical or different and arehydrogen, C₁₋₆alkyl, C₆₋₁₀aryl, (C₆₋₁₀)aryl-(C₁₋₆)alkyl or(C₁₋₆)alkyl-(C₆₋₁₀)aryl, it being possible for the alkyl and/or arylradicals to be substituted by hydroxyl, C₁₋₆alkoxy, C₆₋₁₀aryloxy orhalogen and p and q are 0-12.
 2. A dye compound according to claim 1,wherein X is hydroxy or NHR′ group with R′ being hydrogen, methyl orethyl, and A is of the general formula (IV), (VI), (VII) or (VIII)

wherein R₃ is hydrogen, Y being sulphur, R₆ and R₇ are methyl, and p andq are
 1. 3. A process for the preparation of hydroxy, carboxylicacid/ester or amino functionalized dye compounds of the general formula(I)

with R₁ is C₃₋₁₂ alkylene, C₂ alkoxy-alkylene, C₆₋₁₀ arylene, (C₆₋₁₀)aryl-(C₁₋₆) alkylene or (C₁₋₆) alkyl-(C₆₋₁₀) arylene, the arylene and/orarylene radicals optionally being substituted by hydroxyl, C₁₋₆ alkoxyl,C₆₋₁₀ aryloxy or halogen, X is hydroxy, COOR′ or NHR′ group with R′being hydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or(C₁₋₆) alkyl-(C₆₋₁₀) aryl, the alkyl and/or aryl radicals optionallybeing substituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen,and A is of the general formula, (IV), (V), (VI), (VII) or (VIII)

wherein R₃ is hydrogen, halogen, NR₄R₅, R₄O or R₄S, in which R₄ ishydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₁₋₆)alkyl-(C₆₋₁₀) aryl, the alkyl and/or aryl radicals optionally beingsubstituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen, R₅ ishydrogen, C₂₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₃₋₆alkyl-(C₆₋₁₀) aryl, the alkyl radicals optionally being substituted byC₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen, the aryl radicals optionallybeing substituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen,with the provisio that R₄ is to be chosen first and if R₄ is hydrogen,R₅ can only be hydrogen; Y being sulphur, oxygen or NR₄, with R₄ havingthe meaning given above, R₆ and R₇ are identical or different and arehydrogen, C₁₋₆alkyl, C₆₋₁₀aryl, (C₆₋₁₀)aryl-(C₁₋₆)alkyl or(C₁₋₆)alkyl-(C₆₋₁₀)aryl, it being possible for the alkyl and/or arylradicals to be substituted by hydroxyl, C₁₋₆alkoxy, C₆₋₁₀aryloxy orhalogen and p and q are 0-12, comprising the step of reacting In acondensation reaction the dicarboxylic anhydride of the respective dyemoiety with an aminoalcohol an aminoacid/ester or a diamine comprisingthe respective spacer under polar aprotic conditions.
 4. A colorant forpreparing colored synthetic polymer resins comprising the dye compoundaccording to claim
 1. 5. An ink composition comprising the dye compoundof the general formula (I)

with R₁ is C₃₋₁₂ alkylene, C₂ alkoxy-alkylene, C₆₋₁₀ arylene, (C₆₋₁₀)aryl-(C₁₋₆) alkylene or (C₁₋₆) alkyl-(C₆₋₁₀) arylene, the arylene and/orarylene radicals optionally being substituted by hydroxyl, C₁₋₆ alkoxyl,C₆₋₁₀ aryloxy or halogen, X is hydroxy, COOR′ or NHR′ group with R′being hydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or(C₁₋₆) alkyl-(C₆₋₁₀) aryl, the alkyl and/or aryl radicals optionallybeing substituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen,and A is of the general formula, (IV), (V), (VI), (VII) or (VIII)

wherein R₃ is hydrogen, halogen, NR₄R₅, R₄O or R₄S, in which R₄ ishydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₁₋₆)alkyl-(C₆₋₁₀) aryl, the alkyl and/or aryl radicals optionally beingsubstituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen, R₅ ishydrogen, C₂₋₆ alkyl, C₆₋₁₀ aryl, (C₆₋₁₀) aryl-(C₁₋₆) alkyl or (C₃₋₆)alkyl-(C₆₋₁₀) aryl, the alkyl radicals optionally being substituted byC₁₋₅ alkoxyl, C₆₋₁₀ aryloxy or halogen, the aryl radicals optionallybeing substituted by hydroxyl, C₁₋₆ alkoxyl, C₆₋₁₀ aryloxy or halogen,with the provisio that R₄ is to be chosen first and if R₄ is hydrogen,R₅ can only be hydrogen; Y being sulphur, oxygen or NR₄, with R₄ havingthe meaning given above, R₆ and R₇ are identical or different and arehydrogen, C₁₋₆alkyl, C₆₋₁₀aryl, (C₆₋₁₀)aryl-(C₁₋₆)alkyl or(C₁₋₆)alkyl-(C₆₋₁₀)aryl, it being possible for the alkyl and/or arylradicals to be substituted by hydroxyl, C₁₋₆alkoxy, C₆₋₁₀aryloxy orhalogen and p and q are 0-12.